Diazo-type materials

ABSTRACT

Light-sensitive diazo compositions containing light-sensitive diazonium derivatives of dialkoxy-substituted paraphenylene diamines, at least one coupling component for said diazonium derivatives, and at least one background discoloration inhibitor are disclosed.

United States Patent [72] inventor Robert C. Desjarlais South HadleyFalls, Mass. [21] Appl. No. 667,365 [22] Filed Sept. 13, 1967 [45]Patented Nov. 9, 1971 [73] Assignee The Tecnilax Corporation Holyoke,Mass.

[54] DlAZO-TYPE MATERIALS 39 Claims, No Drawings [52] U.S.Cl 96/75,96/49, 96/91 [51] 1nt.Cl G03c1/60, G03c l/58,G03c 1/54 [50] Field 01Search 96/91, 75, 49

[56] References Cited UNITED STATES PATENTS 1,803,906 5/1931 Kreiger eta1. 96/91 2,531,485 11/1950 Van Glohn et a1 96/91 2,617,726 11/1952Kessels 96/91 X 2,661,291 12/1953 Slifkin. 96/91 X 2,717,832 9/1955Sulich... 96/91 2,893,866 7/1959 Haefeli 96/91 X 3,069,268 12/1962Herrick 96/75 X 3,076,707 2/1963 Lawton et a1. 96/75 3,052,542 9/1962Sulich 96/91 X 3,1 13,025 12/1963 Bialczak 96/49 X 3,248,220 4/1966 VanRhijn 96/91 3,410,688 11/1968 Weleh 96/91 FORElGN PATENTS 937,510 9/1963Great Britain 96/91 OTHER REFERENCES Dinaburg, M. S., PhotosensitiveDiazo Cpds," 1964,

pages 50 53.

Nollev, C. R,, Textbook of Organic Chemistry," 2nd Ed., 1958, page 341Kosar, J., Light-Sensitive Systems," 296.

Primary Examiner- Norman G. TOrChin Assistant ExaminerCharIes L. Bowers,Jr.

Allorneys- William J. Foley, Stanton T. Hadley and John W.

Kane, Jr.

1965, pages 292- ABSTRACT: Light-sensitive diazo compositions containinglight-sensitive diazonium derivatives of dialkoxy-substitutedparaphenylene diamines, at least one coupling component for saiddiazonium derivatives, and at least one background discolorationinhibitor are disclosed.

. BACKGROUND OF THE INVENTION Field of the Invention This inventionrelates to novel, light-sensitive diazotype materials of thetwo-component type which contain a diazonium derivative of adialkoxy-substituted paraphenylene diamine as the diazo component, andwhich are less susceptible to background discoloration after developmentthan are similar materials of the prior art. Certain diazo compositionswithin the scope of this invention are useful in preparing black-lineprints which are highly resistant to light fading and which exhibit aneutral black-line development over a wide image-density range, as wellas being resistant to background discoloration subsequent to theirdevelopment.

DESCRIPTION OF THE PRIOR ART As is well-recognized by those skilled inthe art, the two most widely accepted diazo processes are often referredto as the one-component process or the semi-wet development process,wherein 'the light-sensitive diazotype material contains the diazocompound in the absence of a coupler and the development step in saidprocess consists of applying a developing solution containing a couplerto the diazotype material; and the two-component process or the drydevelopment process, wherein the light-sensitive diazotype materialcontains both the diazo compound and the coupling component orcomponents and wherein the development step in said process consists ofexposing the diazotype material to an alkaline atmosphere, which isusually a mixture of ammonia and water vapors.

Although the two'component or dry development process has certainadvantages over the one-component or semi-wet development process, (themajor advantage being the one most obvious-the fact that it isessentially a dry process), there has, up until now, been certainserious disadvantages associated with the dry process also. In order toobtain certain desired colors in the developed print, it is necessary touse a relatively specific class of diazonium compounds in combinationwith a specific class or classes of coupling components; and, althoughthese combinations may result in the color desired in the final print,this print ofttimes exhibits unacceptable background discoloration inthe exposed areas wherein the diazo component has been decomposed. Thisis particularly true in those cases where the diazo component is adiaionium derivative of a dialkoxy-substituted p-phenylene diamine.Although diazonium derivatives of dialkoxy-substituted p-phenylenediamines are known to be useful as diazo components in diazotypematerials, particularly in one-component diazotype materials, their usein two-component diazotype materials has been severely limited, due tothe pronounced tendency of such materials to discolor after developmentin the background or burnout areas. Without wishing to be bound to anyparticular theory as to the cause of this background discoloration, itis believed that this discoloration is due to the subsequent oxidationof the photolysis products of these types of diazo components (i.e., theinitially colorless derivatives of these diazo components which areformed in the background or nonimage areas upon exposure of thelight-sensitive diazotype material to a light source of sufficientintensity and of the proper wavelength to effect "imaging" of thediazotype material), due to other components and/or impurities which arepresent in the diazo layer. Until now, this problem of backgrounddiscoloration which has been observed with these types of diazocomponents has restricted their use in two-component diazotypematerials, despite the fact that they are in most other respects verysuitable for use in diazotype materials.

In addition, there is also a well-recognized need in the diazo art for adiazotype material which results upon development in aneutral-black-line print which is neutral black over a wide range ofimage densities. Although there are diazotypec materials available whichmay result in a black-line print at a given image density, the color ofthe print may vary considerably from the desired black at higher orlower image densities. It is believed that this two-toning" is due to adifference in the coupling activities of the various couplers employedto obtain a black-line print, and that if the various couplers are notcarefully matched for coupling activity, the difference in couplingrates between or among the coupling components results in images otherthan neutral black, particularly in the lower image density areas.Another factor which makes the achievement of a neutral black-line imageover a wide image density range most difficult is the fact that manyresulting azo dyes produced upon coupling or development of many of thepreviously available diazotype materials are subject to a color-shift ora change in shade with a change in the pH of the diazotype print,resulting in a shift or change in the color of the resulting azo dyefrom the desired neutral black. It is apparent that in order to obtain aneutral black-line print over a wide image density, the coupling ratesof the various couplers employed must be very carefully matched toobtain a mixture of azo dyes in the developed print which is neutralblack over a wide range, and the resulting azo dyes must not be subjectto a color-shift or change in shade with a change in pH. It is, ofcourse, also highly desirable that the burnout or non-image areas ofsuch a neutral black-line print exhibit little or no backgrounddiscoloration upon aging. Until now, a two-component diazotype materialwith these desirable features was unavailable in the diazo art. Asindicated above, although the diazonium derivatives of adialkoxy-substituted p phenylene diamines have heretofore been known tobe capable of producing neutral black-line images over at least someranges of image densities, their inherent tendency to discolor in thebackground or non-image areas has precluded their extensive use in atwo-component diazotype material to form a black-line print.

SUMMARY OF THE INVENTION It has now been found that the incorporation ofat least one background discoloration inhibitor into light-sensitivediazo compositions containing a diazonium derivative of adialkoxysubstituted paraphenylenediamine as the diazo componentsubstantially reduces the background discoloration which one normallyobtains with diazo compositions wherein these types of diazo componentsare employed without such an inhibitor.

7 As has been indicated above, derivatives of dialkoxy-substitutedparaphenyl-enediamines have been found to be a potentially very usefulclass of diazo components, except for their tendency in developed printsto discolor in the background areas. It has been found that this classof diazo compounds is capable of producing azo dyes having excellentlight fastness, bright shades, good resistance to color changes due togas fading; and, with the proper choice of coupling components, dyeswhich form a neutral black image upon development. By incorporating abackground discoloration inhibitor of the type hereinafter disclosed,two-component diazotype materials can be prepared using diazoniumderivatives of dialkoxy-substituted p-phenylenediamines, said diazotypematerials being essentially free from background discoloration afterdevelopment.

DESCRIPTION OF THE PREFERRED EMBODIMENTS The Diazo Component As hashereinbefore been indicated, the light-sensitive com positions of thisinvention employ, as the diazo component, light-sensitive diazoniumcompounds derived from dialkoxysubstituted p-phenylenediamines. Moreparticularly, these diazonium compounds are compounds formed from ap-phenylenediamine having a general formula selected from the groupconsisting of:

( ZtR wherein R is an alkyl group or cycloalkyl group containing fromabout 1 to about 6 carbon atoms, R and R are alkyl groups containingfrom 1 to about 3 carbon atoms, and the group represented by is asaturated, nitrogen-containing, heterocyclic ring, containing up toabout 7 atoms in said ring. Diazonium derivatives of compounds wherein Ris a branched alkyl group, such as isopropyl, isobutyl, secondary butyi,tertiary butyl, tertiary pentyl, 2-pentyl, 3-pentyl, and the like; or acycloalkyl group such as cyclopentyl, cyclohexyl, and the like; andwherein the group represented by diazo compounds are particularly usefulin preparing blackline prints when they are employed with the propercoupling components in a one-component process. However, as has beenindicated above, the use of these compounds in a twocomponent processhas heretofore been limited, due to the fact that the resulting printsexhibited a pronounced degree of background discoloration.

The diazo component employed in the present invention is preferablyemployed in the form of a stabilized diazo salt, such as a metal halidesalt, a sulfate salt, and the like. illustrative of the types ofdiazonium compounds which may be employed in this invention arecompounds such as 4-morpholine-2,5-di

4-1n0rph0lino-2, 5-dl(lsopr0poxy)benzcnc diazoniurn hexafluorophosphate4-morpholno-2, 5-di(eyc1opentoxy) cenzerie diazonium chloride O N N,Cl

and the like.

The Coupling Component As appreciated by one skilled in the art, thechoice of coupler or couplers depends primarily upon the color desiredin the resulting diazo print, and the speed required for development.illustrative of the types of couplers which can be employed in preparingthe diazotype materials of this invention are couplers such asresorcinol, 2-methyl resorcinol, 4-methyl resorcinol, S-methylresorcinol, 2-methyl 4-ethyl resorcinol, 2,4 dichloro resorcinol, 4,6dichloro resorcinol, 4-chloro resorcinol, 4-bromo resorcinol, 4-iodoresorcinol, 4-fluoro resorcinol, N-B-hydroxy-ethyl-a-resorcylamide,a-resorcylamide, N-phenyl a-resorcylamide, resorcinol 5-sulfonic acid,resorcinol 4-sulfonic acid, a-resorcylic acid, resorcinol 4,6 disulfonicacid, resorcinol mono-methyl ether, resorcinol mono benzoate, resorcinolmono acetate, resorcinol mono formate, B-resorcylic acid methyl ester,B-resorcylic acid amide, B-resorcylic acid, a-naphthol B-naphthol 2,3dihydroxy naphthalene, a-resorcylic acid, a-resorcylic acid methylester, a-resorcylic acid amide, 4 bromo-3,5-dihydroxybenzoic acid amide,4-chloro-3,S-dihydroxybenzoic acid amide, bis- (2 ,4-dihydroxy phenylsulfide), bis-( 2,4-dihydroxy phenyl sulfoxide), condensation product ofS-amino resorcinol and cyanuric chloride, hydroquinone monomethyl ether,phloroglucinol, phloroglucinol mono methyl ether, 1,3,5trihydroxy-Z-methyl benzene, 0' hydroxy diphenyl, 3,3',5- trihydroxydiphenyl, 2,4,4'-trihydroxy diphenyl, 2,2',4,4'- tetrahydroxy diphenyl,2,2,4,4'-tetrahydroxy diphenyl sulfide, 3,3',5,5-tetrahydroxy diphenyl,2,2',4,4-tetrahydroxy 3,3'-dimethyl 5,5-dichlorodiphenyl sulfide, 2,2,4,4- tetrahydroxy 5,5dichloro diphenyl sulfide, 2,3 dihydroxynaphthalene 6 sulfonic acid, 1 naphthol-2 sulfonic acid, 1 naphthol-3sulfonic acid, 1 naphthol-4 sulfonic acid, 2 hydroxy naphthalene-3,6-disulfonic acid, 1,8 dihydroxy naphthalene-3,6 disulfonic acid, 2,7dihydroxy naphthalene- 3,6 disulfonic acid, 1,8 dihydroxynaphthalene-3,5 disulfonic acid, l,8 dihydroxy naphthalene-4 sulfonicacid, l,8 dihydroxy naphthalene-3 sulfonic acid, 2,8 dihydroxynaphthalene-6 sulfonic acid, 3,8 dihydroxy naphthalene-6 sulfonic acid 8acetylamino-l -naphthol-5-sulfonic acid, 2 hydroxy naphthalene--sulfonicacid, 2 hydroxy naphthalene-4-sulfonic acid, 2 hydroxynaphthalene-6,8-disulfonic acid, 2 hydroxy naphthalene-7-sulfonic acid,1 hydroxy naphthalene- 3,8-disulfonic acid,2 hydroxy-3naphthoic-(3'nitro) anilide, 2 hydroxy-3 naphthoic-(4'chloro) anilide, 2hydroxy-3 naphthoic-(4chloro) anilide, 2 hydroxy-3 naphthoic- (4methoxy)anilide, 2 hydroxy-3 naphthoic- (Zmethoxy) anilide, 2hydroxy-3naphthoic-(2 methyl) anilide, 2 hydroxy- 3 naphthoic-(4 methyl) anilide,2 hydroxy-3 naphthoic-(S' methyl) anilide, 2 hydroxy-3 naphthoic-( 2',5'dimethoxy) anilide, 2 hydroxy-3 naphthoic-(l naphthanilide), 2 hydroxy-3naphthoic-( 2 naphthanilide), 2 hydroxy-3 naphthoic-(Z methyl, 4'chloro) anilide, 2 hydroxy-3 naphthoic-(Z chloro) anilide, (acetoacetylamino benzene), (acetoacetyl-benzylamide), (2 acetoacetylamino-l-methoxybenzene), (2 chlorolacetoacetylamino-benzene (4-chlorol-acetoacetylaminobenzene), (2,5-dichlorol -acetoacetylamino-benzene (4acetoacetylamino-l ,B-dimethoxy benzene), (6acetoacetylamino-l,4-dimethoxy benzene), (6 chloro-4 R4 OH OH R4 110- -sOH I z z R HO OH R4 0 HO -& OH

wherein R is hydrogen; an alkyl group containing from one to about sixcarbon atoms, such as methyl, ethyl, propyl, butyl, amyl, hexyl,2-ethylbutyl, and the like; and unsubstituted aryl group orhalo-substituted substituted aryl group such as pchlorophenyl,m-chlorophenyl, phenyl, and the like; an aralkyl group, includingalkyl-substituted arlkyl groups and halo-substituted aralkyl groups,such as benzyl p-methylbenzyl, pchlorobenzyl, o-chlorobenzyl and thelike; an alkaryl group, including halo-substituted alkaryl groups, suchas xylyl, chloroxylyl, tolyl, chlorotolyl, and the like; an alkoxy groupcontaining from one to about six carbon atoms, such as methoxy, propoxy,butoxy, amyloxy, and the like; an aryloxy group includinghalo-substituted aryloxy groups such as phenoxy, p-chlorophenoxy and thelike, an aralkyoxy group including halo-substituted aralkoxy groups suchas benzyloxy, p-chlorobenzyloxy, and the like; or a halogen, such aschlorine, bromine or iodine; Z is hydrogen or a halogen, such aschlorine, bromine or iodine, and wherein at least one of the groupsrepresented by R and Z is a group other than hydrogen. The substituteddiresorcyl sulfides are particularly preferred.

The substituted diresorcyl sulfides described above onto prepared byreacting sulfur dichloride in the presence of an inert solvent with aresorcinol substituted in the 2-position with an alkyl group, suchasmethyl group, an ethyl group, a propyl group, a butyl group, an amylgroup, a 2-ethyl-butyl group, and the like; an aryl group orhalo-substituted aryl group, such as a phenyl group, a p-chlorophenylgroup, a mchlorophenyl group, and the like; an aralkyl group,alkyl-substituted aralkyl group, or halo-substituted aralkyl group suchas a benzyl group, a p-methylbenzyl group, a p-chlorobenzyl group, ano-chlorobenzyl group, and the like; and alkaryl group orhalo-substituted alkaryl group, such as a xylyl group, a chloroxylylgroup, a tolyl group, a chlorotolyl group, and the like; an alkoxygroup, such as a methoxy group, a propoxy group, a butoxy group, anamyloxy group, and the like; an aryloxy group or halo-substitutedaryloxy group, such as a phenoxy group, a p-chlorophenoxy group, and thelike; an aralkoxy group or halo-substituted aralkoxy group, such as abenzyloxy group, a p-chlorobenzyloxy group, and the like; or a I halogroup, such as a chloro group, an iodo group, a bromo group, and thelike; a resorcinol substituted in the 4-position with a halo group, suchas a chloro group, an iodo group, a

- bromo group, and the like; or a resorcinol substituted in the 2-position with an alkyl group, such as a methyl group, an ethyl group, apropyl group, a butyl group, an amyl group, a 2-ethylbutyl group, andthe like; an aryl group or halo-substituted aryl group, such as a phenylgroup, a p-chlorophenyl group, a m-chlorophenyl group, and the like; anarlkyl group, alkylsubstituted aralkyl group, or halo-substitutedaralkyl group such as a benzyl group, a p-methylbenzyl group, apchlorobenzyl group, an o-chlorobenzyl group, and the like; and alkarylgroup or halo-substituted alkaryl group, such as a xylyl group, achloroxylyl group, a tolyl group, a chlorotolyl group, and the like; analkoxy group, such as a methoxy group, a propoxy group, a butoxy group,an aryloxy group, and the like; an aryloxy group or halo-substitutedaryloxy group, such as a phenoxy group, a pchlorophenoxy group, and thelike; an aralkoxy group or halo-substituted aralkoxy group, such as abenzyloxy group, a p-chlorobenzyloxy group and the like; and in the4-position with a halo group, such as a chloro group, an iodo group, abromo group, and the like. lnert solvents such as diethyl ether,dipropyl ether, ethyl acetate, and the like, can be employed, and thereaction temperature can vary, depending on the type of inert solventwhich is employed. Temperatures of from about 5 C. to about 35 C. arepreferred, with temperatures of from about 5 to about 15 C. beingparticularly preferred with the lower-boiling inert solvents. It is alsopreferred to conduct the reaction under an atmosphere of a dry, inertgas, such as nitrogen, helium, and the like, said gas being used tofacilitate the removal of the hydrogen chloride which is evolved. Theresulting substituted diresorcyl sulfide compounds are easily recoveredas crystalline solids having relatively high melting points (in excessof 150 C.) and are readily purified by recrystallization from alcoholsor ketones, such as acetone and methylethyl ketone. The sulfoxidederivatives of these substituted diresorcyl sulfides are prepared bytreating the sulfide with an oxidizing agent, such as hydrogen peroxide,chromic oxide, potassium permanganate, and the like. Illustrative of thetypes of compounds within this preferred class of orange or sepiacouplers are compounds such as ,4,4-tetrahydroxy-3,3'-dimethyldiphenylsulfide, ,4,4'-tetrahydroxy-5,5-dichlorodiphenyl sulfide, ,4,4'-tetrahydroxy-3,3-dimethyl-5,5-dichlorodiphenyl sulfide,,4,4'-tetrahydroxy-3,3,'-dimethyldiphenyl sulfoxide, and the like. It isbelieved that the diresorcyl sulfides and sulfoxides which aresubstituted in both the 3,3 positions and the 5,5 positions are novelcompositions of matter, and they are claimed as such herein. Quiteunexpectedly, they have been found to be excellent yellow shadingcomponents for diazo compositions, and they exhibit coupling rates whichare highly compatible with the coupling rates of the blue couplers whichare usually employed.

The following preparations are provided to illustrate more specificallythe methods of preparing the preferred orange or sepia couplers for usein the present invention.

A. PREPARATION OF ,4,4'-TETRAHYDROXY-3,3 DIMETHYL DlPHENYL SULFIDE 18.7grams of Z-methyl resorcinol were dissolved with stirring in 48 ml. ofethyl acetate. A solution of 7.8 grams of sulfur dichloride in 58 ml.ethyl acetate was then added slowly to the in warm toluene, filtered anddried to yield 7.5 grams (36 percent of theoretical) of a product whichwas insoluble in cold water, toluene and benzene and soluble in alcoholsand ketones and which had a melting point of l68-l70 C. The2,2-4,4'-tetrahydroxy-3,3'-dimethyl diphenyl sulfide product gave apositive test for sulfur and analyzed as follows: Carbon59.61(theoretical 60.41 );Hydrogen:5.28(Theoretical: 5.07).

B. PREPARATION OF 2,2',4,4'3,3'-

DIMETHYL DIPHENYL SULFOXIDE 13.9 grams of2,2,4.4'-tetrahydroxy,3.3-dimet.hyl diphenyl sulfide were added, withstirring, to 100 ml. of glacial acetic acid. 5.65 grams of 30 percentH,O, were then added slowly to the solution while stirring wascontinued. The temperature rose to 40 C. then slowly subsided to 25 C.Stirring was continued for 24 then the reaction mixture was diluted with250 ml. of water. The diluted reaction mixture was stirred for anadditional hour, during which a precipitate separated from the reactionmixture. The precipitate was filtered, washed with water, and dried toyield 8.5 grams of a product which decomposed at 145 C. The2.2',4,4'-tetrahydroxy,3,3'-dimethyl diphenyl sulfoxide product analyzedas follows: Carbon:56.98(Theoretical:57.13); 5.15(Theoretical:4.79)

C. PREPARATION OF 2,2',4,4'5,5'-

DICHLORODIPHENYL SULFIDE 21.7 grams of 4-chlororesorcinol were dissolvedin 58 cc. of cold ethyl acetate (15 C.), and then to this4-chlororesorcinolethyl acetate solution was slowly added a solution of7.8 grams of sulfur dichloride in 58 cc. of ethyl acetate. Thetemperature during the addition was maintained at 10 to C. Uponcompletion of the addition of the sulfur dichloride solution to the4-chlororesorcinol solution, the reaction mixture was stirred overnight.After stirring was completed, the reaction mixture was just washed with100 cc. of water, and then with 100 cc. of 5 percent sodium bicarbonatesolution to neutralize any of the remaining hydrochloric acid which wasformed during the reaction. The solvent fraction was separated from theaqueous layer, and the ethyl acetate solvent was evaporated. The solidresidue which remained was slurried in water to remove any unreacted4-chlororesorcinol which may have been present, and the solids were thancollected by filtration. The collected solids were slurried with hottoluene, filtered while hot, and then air dried to yield 7.3 grams of awhite solid which melted at 220 to 222 c. The2,2',4,45,5-dichlorodiphenyl sulfide product had the followingCarbon-Hydrogen analysis: Carbonz44.80(Theoretical:45.20); Hydrogen217(Theoretical:2.51 Infrared analysis of the product was as follows:

Medium-OH absorption band at 2.95 microns Strong-OH absorption band at3.01 microns Phenyl absorption bands at 6.2 microns, 6.26 microns,

and 6.33 microns.

D. PREPARATION OF 2,2',4,4'3,3'-

DIMETHYL-5,5'-DICHLORODIPHENYL SULFIDE l 1.5 Grams of2-methyl-4-chlororesorcinol were dissolved in 75 cc. of ethyl acetateand 3.75 grams of sulfur dichloride were added, with stirring, to the2-methyl-4-chlororesorcinolethyl acetate solution over a 30 minuteperiod. During the addition of the sulfur dichloride, the temperature ofthe reaction mixture was maintained at 15 C. and, upon completion of theaddition of the sulfur dichloride, the reaction mixture was stirred foran additional hour. The ethyl acetate was then evaporated from thereaction mixture, and the residue was washed with 100 cc. of toluene. Awhite solid was collected by filtration and dried to yield 7. 2 grams ofa product which had a melting point of 198 to 200 C. The2,2,4,4'-tetrahydroxy- 3,3-dimethyl-5,5'-dichlorophenyl sulfide productanalyzed as follows:

Carbon:48.77(Theoretical:48.4); Hydrogen 5.55(Theoretical:3.46).Infrared analysis was as follows:

Medium-OH absorption band at 2.88 microns Weak-OH absorption band at 290microns Strong phenyl absorption band at 6.28 microns Strongsulfur-phenyl absorption band at 9.23 microns Strong chlorine absorptionband at 13.5 microns.

The substituted diresorcyl sulfide couplers and their sulfoxidederivatives described above, have been found to be fast yellow couplingcomponents for the diazonium derivatives of the dialkoxy-substitutedparaphenylene diamines which are used as the diazo components of thisinvention, and they produce diazo prints which exhibit improvedresistance to fade under the influence of ultraviolet radiation andvisible light. The use of these couplers with the preferred bluecouplers described below produces neutral black-line diazo prints havinga wide range of densities. The advantages of such compounds over thosepresently available will be apparent to those skilled in the art, sinceit has heretofore been difficult to obtain a neutral black-line diazoprint over a wide density range, particularly with only two couplingcomponents.

The preferred blue couplers for use in the present invention are3'-suhstituted, 2-hydroxy, 3naphthanilides wherein the substituent inthe 3'-position is a non-chromophoric, electronwithdrawing substituentin the meta position of the aniline 'nucleus, i.e., compounds having thegeneral formula ((H3OCH;)

a carbethoxy group 0 (("J-OCH,CH;)

a carbopropoxy group H (-co 013,011,031)

a carbobutoxy group and the like; sulfarnyl groups, includingN-substituted sulfamyl groups for example, a methylsulfamyl group abenzylsulfamyl group an allylsulfamyl group H s0,N

CH,CH=CH, a morpholinopropylsulfamyl group a benzylcarbamyl group amorpholinocarbamyl group and the like; and acyl groups, for example, anacetyl group O (OH L) a propionyl group (CH3CH:( a butyryl group and thelike. Compounds wherein X is a trifiuoromethyl group, an unsubstitutedsulfamyl group, or an aliphatic acyl group, such as an acetyl group areparticularly preferred. Those 3'-substituted 2-hydroxy, 3-naphthanilideswherein the non-chlomophoric and electron-withdrawing substituentrepresented by X contains a sulfonyl group or carbonyl group attacheddirectly to the aniline nucleus are believed to be novel compositions ofmatter, and are claimed as such in a separate application filed on evendate as the present application, U.S. Serial No. 667,372. g

The preferred 3-substituted, 2-hydroxy, B-naphthanilides described abovecan be prepared either by reacting a metasubstituted aniline having theformula a benzoyl group wherein X is as hereinbefore defined with2-hydroxy, 3- naphthoyl chloride in the presence of a suitable solvent,or by reacting such a meta-substituted aniline with 2-hydroxy-3-naphthoic acid in the presence of an inert solvent and phosphorustrichloride. Illustrative of the meta-substituted anilines which can beemployed in preparing these preferred blue couplers are compounds suchas m-(trifluoromethyl) aniline (HMO-C a) methyl m-aminobenzoatc ethyln-aminobenzoato propyl m-mninobcnzoatc butyl m-aminobcnzontcm-aminobenzenesulfonamidc (I-IZN 40 N11 N-me thyl-m-aminobenzenesulfonamide /H --s OgN N-benzyl-m-aminobenzenesulfonamideN-allyl-m-aminobenzenesulfonamide /H s0,N

C H; C H2 N-morpholinopropyl-m-aminobenzene-sulfonamide HgN CH CII CII NO m-aminobenzamide N -methyl-m-aminobenzamide o H IIN-benzyl-m-aminobenzamide m-aminobenzmorpholide prpy1m-aminophenylketone phenyl-m-aminophenyl ketonc and the like.

When the preferred 3'-substituted, 2-hydroxy, 3-naphthanilides areprepared by reacting a meta-substituted aniline with 2-hydroxy,3-naphthoyl chloride, the meta-substituted aniline is first dissolved ina solvent such as toluene, dioxane, methylene chloride, pyridine, andthe like, and then 2-hydroxy, 3-naphthoy1 chloride is added to theaniline solution. The resulting reaction mixture is stirred overnight,and then the desired 3'-substituted, 2-hydroxy, 3-naphthanilide reactionproduct is isolated in the usual manner. The reaction between themeta-substituted aniline and Z-hydroxy, 3-naphthoyl chloride can beaccelerated by refluxing the reaction mixture,

and the yield of the desired 3'-substituted, 2-hydroxy, 3-'

naphthanilide can be improved by incorporating an acid acceptor in thesaid reaction mixture. In many instances the solvent used to dissolvethe meta-substituted aniline reactant can also serve as an acid acceptor(e.g., solvents such as pyridine, picoline, triethylamine, and thelike), or the m-substituted aniline can itself serve as an acidacceptor, if it is employed in amounts in excess of the theoreticalamount necessary to react with all of the 2-hydroxy, 3-naphthoylchloride present in the reaction mixture.

When the preferred 3'-substituted, Z-hydroxy, B-naphthanilides areprepared by reacting a meta-substituted aniline with 2-hydroxy,3-naphthoic acid in the presence of an inert solvent and phosphorustrichloride, 2-hydroxy, B-naphthoic acid and the m-substituted anilineare first dissolved or slurried in a relatively inert solvent such astoluene, methylene chloride, dichloroethane, and the like; and thenphosphorus trichloride is added at a controlled rate in order to preventthe temperature of the reaction mixture from exceeding about 55 C. Uponcompletion of the addition of the phosphorus trichloride the reactionmixture is then refluxed until substantially all of the hydrochloricacid formed from the reaction is driven off. The desired 3'-substituted,2-hydroxy, 3-naphthanilide reaction product can be isolated from thereaction mixture by direct filtration if it has precipitated fromsolution during the course of the reaction; otherwise it can be isolatedby cooling, or by the addition of solvents in which the desired productis known to be insoluble.

1 2 Illustrative preparations of the preferred 3'-substituted, 2-hydroxy, B-naphthanilides are as follows:

A. PREPARATION OF Z-HYDROXY, 3-NAPHTHOIC ACID.

3'-(SULFONAMIDO) ANILIDE SIOQNIII BY REACTING m-AMINOBENZENESULPONAM IDEWITH Z-HYDROXY, B-NAPHTHOYL CHLORIDE 17.2 grams ofm-aminobenzenesulfonamide were dissolved in ml. of dry pyridine. 20.6grams of 2-hydroxy, 3- naphthoyl chloride which was prepared byrefluxing Z-hydroxy, 3-naphthoic acid and thionyl chloride in methylenechloride, were then added to the aminobenzenesulfonamidepyridinesolution. Upon completion of the addition of napththoyl chloride to theaminobenzenesulfonamidepyridine solution, the resulting reaction mixturewas refluxed for 2 hours at 1 18 C. The reaction mixture was then cooledto room temperature and 500 ml. of water were added. The 2- hydroxy,3-napthoic acid, 3'(sulfonamido) anilide reaction product precipitatedin the form of a cream colored solid. After filtering, the solids werewashed with water, slurried in isopropanol, and then re-filtered. Theyield was 21.5 grams of a white solid having a melting point of 276 to280 C. Carbonhydrogen-nitrogen analysis of the product was as follows:

Found Theoretical Hydrogen 4.31% 0% Nitrogen 7.64% 8.20% Carbon 62.21%59.60%

Infrared analysis was as follows:

Strong amide absorption bands at 6.0 and 6.5 microns. Strong sulfonamideabsorption bands at 6.98, 7.55 and 8.67

microns. Medium-NH and absorption bands at 3.0 microns.

Weak-NH: bands absorption at 3.1 microns. B. PREPARATION OF Z-HYDROXY,B-NAPHTHOIC ACID 3'-(TRIFLUOROMETHYL)ANILIDE BY REACTING 2-HYDROXYL,B-NAPI'ITHOIC ACID WITH m-(TRIFLUOROMETHYL)ANILINE IN THE PRESENCE OFPHOSPHORUS TRICHLORIDE Found Theoretical Hydrogen 3.39% 3.64% i Nitrogen3.49% 4.24% 1 Carbon 64,57% 65.l%

lnfrared analysis was as follows:

Amide absorption bands at 7.60 and 14.35 microns. I

Trifluoromethyl absorption bands at 7.50, 8.54 and 8.90 0

microns.

preparations set forth above are compounds such as 2-hydroxy,3-naphthoic acid, 3-(acetyl)anilide OH O=C-CH3 2-hydroxy,3-naphthoicacid,3 (N-allylsulfonamido) anilide H A OH S|O N CHgCH=CHg JiH Q2-hydroxy, 3-naphthoic acid, 3(N-benzylsulfonamid0) anilide H OII SIOQNQ WQ 0 H 2-hydr0xy, 3-naphbhoic acid, 3 (N-morpholinopropylsulfonamido)anilide H on SIOZN/ OILCH OH N b w n-Q w 0 H 2-hydroxy, 3naphthoic acid,3(N-methylsulfonamido) anilide H OH SJO N c N 1Q 0 H and the like.

THE BACKGROUND DISCOLORATION INHIBITORS The background discolorationinhibitors which have been found to be useful in preventingdiscoloration in the burnout or background areas of the developeddiazotype materials of this invention are N,N'Diaryl-substuted alkylenediamines, including N,N methylene bridge tertiary amino derivativesthereof. These inhibitors have a general formula selected from the classconsisting and A1NR NAr wherein Ar is a group selected from the classconsisting of a phenyl group and a hydrocarbyl-substituted phenyl groupwherein said hydrocarbyl substituents are in either the meta or paraposition; R is a divalent hydrocarbon radical having a chain of eithertwo r0 three carbon atoms separating the nitrogen atoms of the diamine;R is a group selected from the class consisting of hydrogen, alkylgroups containing from one to five carbon atoms, aralkyl groupscontaining from seven to about 10 carbon atoms, and groups representedby Ar; and R is selected from the class consisting of a methylene groupand hydrocarbyl-substituted methylene groups. Compounds wherein Ar is aphenyl group, m-tolyl group or p-tolyl group;

' R is an ethylene group, a methyl-substituted ethylene group. a

1,2-dimethyl-substituted ethylene group or an ethyl-substituted ethylenegroup, a phenyl-substituted ethylene group; R is hydrogen; and R is amethylene group or a phenyl-substituted methylene group are preferred.Illustrative of such compounds are compounds such asN,N'-diphenylethylenediamine N,N'di (m-tolyl) ethylene diamine CH3 (3H3N,N di(p-to1yl) ethylene diamine N,N-diphenyl, 1,2-bubylenediamine HgCH:

N,N-diphenyls tyrenediamine 1 2 ,8-triphenylimidazolidine e 1 ,3-di(p-tolyl) -2-phenylimidazolidine 1,2,3-tripheny1, 4 -methy1imidazo1idine1,2,3-triphenyl, 4,5 dimebhylimidazolidine r CH; CH;

1,2,3-triphenyl, 4-ethylimidazolidiue 1,2,3,4,tetraphenylimidazolidineand the like.

Although the amount of inhibitor which is employed in a coatingcomposition has not been found to be narrowly critical from about 0.10part by weight of inhibitor per parts by volume of the coating mixtureto about 2.0 parts by weight of inhibitor per 100 parts by volume of thecoating mixture is preferred, with about from 0.25 part by weight toabout 1.0 part by weight being particularly preferred. Mixtures of thesebackground discoloration inhibitors may also be employed, as well asmixtures of these types of inhibitors with other types of inhibitors orantioxidants.

Inhibitors having the general formula:

wherein Ar, R and R are as hereinbefore defined can be prepared byreacting an aromatic amine such as aniline, para toluidine,meta-toluidine, and the like, with a dihalo-substituted alkane oraralkane, such as ethylene dichloride; 1,2, dibromobutane; 2,3dibromobutane; 1,2 dibromopropane; styrene dibromide and the like. Thisreaction is a known reaction (of, for example, Bennett, G.M. Journal ofthe Chemical Society" 1919, 115, 577), and can be illustrated by thegeneral equation:

wherein Ar, R and R are as hereinbefore defined and X represents ahalogen, such as bromine, chlorine, and the like. The reaction is morespecifically illustrated by the following preparation:

PREPARATION OF N,N'Dl-( p-TOYL) ETHYLENE DlAMlNE 42.8 Grams ofpara-toluidine,

(0.4 mole) were added to 9.9 grams of ethylene dichloride, C1-CH -Cl-l-Cl, (0.1 mole); and the mixture was heated to reflux with stirring. AtC. a heavy precipitate began to form, and the mixture reached refluxtemperature at C. After refluxing at 150 C. for 2 hours, the mixture wascooled to room temperature, at which temperature the reaction mixturewas a solid. The solid reaction mass was then stirred with 200 ml. ofwater and filtered. A brownish-yellow solid as recovered andrecrystallized from hexane to yield 13 grams of a white solid whichmelted at 89 to 92 C. The N,N'di(ptolyl)ethylenediamine product had thefollowing carbonhydrogen-nitrogen analysis:

tolyl)ethylenediamine product was as follows:

Strong secondary amine absorption band at 2.95 microns.

Strong absorption band at 6.56 microns.

Very Strong-Cl-Q-absorption band at 6.85 microns. Para-substituteddoublet absorption bands at 12.34 microns l and 12.42 microns.inhibitors having the general formula wherein Ar, R and R are ashereinbefore defined can be prepared by reacting an aldehyde of theformula R"CHO wherein R is a hydrocarbyl group with anN,N'-diaryl-substituted alkylene diamine of the general formula:

Ar-Nl-l-R -NH-Ar wherein Ar and R are as hereinbefore defined. Forexample, as disclosed by Moos in Berichte Der Deutchen Chemischen 1Gesellschaft, Vol. 20, page 732, l,2,3-triphenylimidazolidine i can beprepared by heating benzaldehyde with N,N-diphen-i ylethylenediamine toboiling temperatures. The resulting imidazole derivative can be purifiedby recrystallization from alcohol, petroleum ether, benzene or othersuitable solvents. inhibitors such asl,3-di(m-toyl)-2-phenylimidazolidine andil,3-di(p-toyl)-2-phenylimidazolidine can be prepared in an! analogousmanner by substituting N,N-di(m- 1' tolyl)ethylenediamine andN,N'-di(p-tolyl)ethylenediamine I for N,N'-diphenylethylenediamine inthe procedure set forth above. A general equation for the reaction is asfollows: i

Ar Ar NR5-N\ R3CH0 ArN R NAr H2O H II CH 1 40 wherein Ar, R and R" areas hereinbefore defined and the divalent group is equivalent to thegroup R as hereinbefore defined. The reaction is more specificallyillustrated by the following preparation:

PREPARATION OF l,2,3,-TRIPHENYL1M1DAZOLIDENE 21.2 Grams ofdiphenylethylenediamine,

Found Theoretical Nitrogen 9.38 9.33 Carbon 83.71 84.0 Hydrogen 6,846.66

The infrared analysis of the product was as follows: N o

absorption bands.

Strong phenyl ring absorption band at 6. 25 microns.

Very Strong phenyl ring absorption band at 6.64 microns.

The light-sensitive diazo compositions of this invention can alsocontain any of the additional components which are often employed insuch compositions, such as stabilizers for the diazo compound present insaid compositions. The diazo composition is usually applied to asuitable base support in the form of a solution of various components ina solvent or solvents, which is then dried to form a coated supportmaterial which can be imaged and developed in the well-known manner ofthe diazotype art. The support may be any of the well-known supportmaterials employed for diazo compositions, such as paper, cloth,transparentized paper, cellulose ester and ether films and polyesterfilms having a subcoat thereon, such as mylar film having a subcoat ofcellulose acetate butyrate.

The diazo coating compositions of this invention can be used to preparelight-sensitive diazotype materials, which are new and useful productsfor use in the fields of engineering drawing reproduction, microfilmvisual communications and the graphic arts.

The following examples will serve to further illustrated this invention,but they are not intended to limit the scope thereof in any way.

EXAMPLE I A light-sensitive coating formulation was prepared containingthe following components:

This coating formulation was coated onto a clear, cellulose diacetatebase and dried. The dried, light-sensitive film was then exposed under amercury vapor lamp light-source in a diazo duplicating machine using asilver halide master. The exposed film was then developed with ammoniavapor. A neutral black print over a wide range of image densities wasobtained, and the resulting print exhibited excellent light-faderesistance and aging characteristics. Similar results are obtained whencompounds such as N,N-diphenylethylenediamine, N,N-di(p-tolyl)ethylenediamine, N,N-di(m-tolyl) ethylene diamine,l,3-di(p-tolyl)-2-phenylimidazolidine imidazolidine and1,3,-di(m-tolyl)-2-phenylimidazolidene are substituted forl,2,3-triphenylimidazolidine in the formulation set forth above.However, if the N,N'-diaryl-substituted alkylene diamine backgroundinhibitors are omitted from the formulation set forth above, anobjectionable, reddish background appears in the background or burn-outareas of the developed print upon aging of the print. The amount ofbackground discoloration which was observed with the above formulationswas measured with a photovolt brightness meter, using White Cararraglass as the brightness standard. The background discoloration due tonatural aging of the films prepared from the above formulations was asfollows:

Initial After 5 Formulations (identified by inhibitor) brightness months1.2 3-triplmnylimidszolidine 75. 72. "-dimcthylethylene diainine... 75.073.0 N, -di(p-tol vl)ethylone diainino 75. 0 74. 0N,N'-di(m-t0lyl)ethyleno diamlno. 75.0 73.0 1,3-dip-tolyl)-2-phenylimidazolldi1 75.5 73. 5 l.3-di(n1-tolyl)-2phtnylimidazolidino. 75.0 72.5 (ontrol (no N,N-dinryl-substitut0d nlkylono(limninc inhibitor) T5. 5 l til. 0

I With rod discoloration observed.

The results set forth above clearly indicate that theN,N-diaryl-substituted alkylene diamine inhibitors substantially reducethe amount of background discoloration which is normally obtained withtwo-component diazo-type materials wherein a diazonium derivative of adialkoxy-substituted paraphenylene diamine is employed as the diazocomponent.

EXAMPLE 2 A light-sensitive coating formulation was prepared containingthe following components:

This coating formulation was coated onto a clear cellulose diacetatefilm base and dried. The dried, light-sensitive film was then exposedand developed in a manner similar to that set forth in example i. Aneutral black print was obtained from this film over a wide range ofimage densities, and the resulting print exhibited excellent light-faderesistance and aging characteristics.

EXAMPLE 3 A light-sensitive coating formulation was prepared containingthe following components:

COMPONENT AMOUNT Methanol 52 cc.

Acetone 38 cc. Methyl ethyl ketone cc. Hexafluorophosphuric acid 0.6 cc.Thiourea 0.6 g.

2 Hydroxy-3-naphthoic acid (J'acctyUanilide 0.99 g.2,2.4.4'-Tctrahydroxy-3.3'-dimethyldiphenyl sulfide 0.75 g. l.2,."itriphcnylimidazolidine 0.75 g. 4 Murpholino-2.5-diisopropoxybenzenediazonium hexafluorophosphute 13 g.

This coating formulation was coated onto a clear, cellulose diacetatefilm base and dried. The dried, light-sensitive film was then exposedand developed in a manner similar to that set forth in example 1. Aneutral black print was obtained from this film over a wide range ofimage densities, and the resulting print exhibited excellent light-faderesistance and aging characteristics. When the2,2',4,4'-tetrahydroxy-3,3'- dimethyldiphenyl sulfide coupler isreplaced with either 2,2,4,4'3,3'-dimethyldiphenyl sulfoxide or2,2',4,43.3-dimethyl5,5'-dichlorodiphenyl sulfide in the aboveformulation, similar results are obtained, in that an excellent blackprint from the film is obtained over a wide range of image densities,and s aid print is resistant to subsequent background discoloration inthe burn-out" areas.

Similarly, when the 4-morpholino-2,5-diisopropoxybenzene diazoniumhexafiuorophosphate is replaced with either 4- morpholino-2,S-dicyclopentyloxybenzene diazonium hexafiuorophosphate or4-morphoIino-2,5-di(secondary-butoxy) benzene diazoniumhexafluorophosphate in the above formulation, the desirable propertiesare also observed in the prints resulting from films prepared from saidformulations. When the 2,2',4.4-tetrahydroxy-3.3-dimethyl dlphenylsuliide coupier in the above formulation is replaced with dlresorcylsultide, dlresorcyl suli'oxlde or dlresorclnol. the prints resultingfrom the films prepared these formulations are also resistant tobackground discoloration. but blue, violet, or blue-black prints havingreddish violet hues are obtained. rather than the neutral 1 5 blackswhich are obtained from formulations containing the preferred orange orsepia couplers.

We claim:

1. A light-sensitive diazo composition which comprises:

A. at least one light-sensitive 2,5-dialkoxy-4-aminobenzene diazoniumcompound [derived from a dialkoxy-substituted-p-phenylene diamine]having the general formula selected from the class consisting of:

1 O R R I and g g R JN -N,Y 3 5 wherein Y is an inorganic acid anion; Ris an alkyl group or a cycloalkyl group containing five or six carbonatoms; R and R are alkyl groups containing from one to three carbonatoms, and the group represented by is a saturated, nitrogen-containing,heterocyclic ring containing six atoms in said ring;

B. at least one azo coupling component for said diazonium compound;

C. at least one background discoloration inhibitor having a generalformula selected from the class consisting of:

5 5 Ar Ar \N-R5-N Rs u Ar-N-R-NAr wherein Ar is a phenyl group or analkyl-substituted phenyl group wherein said alkyl substituents are ineither the meta or para position, R" is a divalent hydrocarbon radicalhaving a chain of two or three carbon atoms separating the nitrogenatoms in said inhibitor, wherein R is a hydrogen atom, an alkyl groupcontaining from one to five carbon atoms, an aralkyl group containingfrom seven to 10 carbon atoms.

2. A light-sensitive diazo composition as claimed in claim 1 wherein thelight-sensitive diazonium compound is [derived from4-morpholino-2,5-diisopropoxyaniline, 4-morpholino- 2,5-di(tertiarybutoxy) aniline; 4-morpholino-2,5-di,(secondary butoxy) aniline; or4-morpholino-2,5'dicyclopent0xyaniline] a4-morpholin0-2,5-di(isopropoxy) benzene diazonium salt, a4-morpholino-2,5-di(tertiary butoxy) benzene diazonium salt, a4-morpholino-2,5-di(secondary butoxy) benzene diazonium salt or a4-morpholino-2,5-di(cyclopentoxy) benzene diazonium salt.

3. A light-sensitive diazo composition as claimed in claim 2 whichcomprises as a background discoloration inhibitor at least one compoundselected from the class consisting of N,N'-diphenylethylenediamine,N,Ndi(m-tolyl) ethylene diamine, N,Ndi(p-tolyl) ethylenediamine,N,Ndiphenylpropylenediamine, N,Ndiphenyl-2,3-butylenediamine, N,N-diphenyl-l ,Z-butylenediamine, N,N-diphenylstyrenediamine,l,2,Striphenylimidazolidene, l,3-di-(m-tolyl)-2-phenylimidazolidene, andl,3-di(p-tolyl)-2-phenylimidazolidene, l,2,3-triphenyl-4-methylimidazolidene, l,2,3triphenyl4,5-dimethylimidazolidine, l,2,3-triphenyl-4-ethylimidazolidine, andl,2,3,4-tetraphenylimidazolidine.

4. A light-sensitive diazo composition as claimed in claim 3, wherein atleast one of the compound is a compound having the general formulaselected from the class consisting of:

wherein R is selected from the class consisting of hydrogen alkyl groupscontaining from one to six carbon atoms, unsubstituted aryl groups,halo-substituted aryl groups; unsubstituted aralkyl groups, aralkylgroups having alkyl substituents on the aryl portion thereof, aralkylgroups having halo substituents on the aryl portion thereof,unsubstituted alkaryl groups, alkaryl groups having halo substituents onthe alkyl portion thereof, alkoxy groups containing from one to sixcarbon atoms, unsubstituted aryloxy groups, halo-substituted aryloxygroups, unsubstituted aralkoxy groups, aralkoxy groups having halosubstituents on the aryl portion thereof, and halogen atoms; Z isselected from the class consisting of hydrogen and halogen atoms; andwherein at least one of the groups represented by R and Z is a groupother than hydrogen.

5. A light-sensitive diazo composition as claimed in claim 4 wherein Ris methyl.

6. A light-sensitive diazo composition as claimed in claim 3 wherein atleast one of the coupling components for the diazonium compound is acompound having the general formula:

wherein X is a non-chromophoric, electron-withdrawing substituent and isselected from the class consisting of trifluoroalkyl groups, carbalkoxygroups, the sulfamyl group, N-substituted sulfamyl groups, the carbamylgroup, N-substituted carbamyl groups and acyl groups.

7. A light-sensitive diazo composition as claimed in claim 3 wherein thecoupling component for the diazonium compound is a mixture of A) acompound having the general formula selected from the class consistingof:

and

wherein R is selected from the class consisting of hydrogen, alkylgroups containing from one to six carbon atoms, unsubstituted arylgroups, halo-substituted aryl groups; unsubstituted aralkyl groups,aralkyl groups having alkyl substituents on the aryl portion thereof,aralkyl groups having halo substituents on the aryl portion thereof,unsubstituted alkaryl groups, alkaryl groups having halo substituents onthe alkyl portion thereof, alkoxy groups containing from one to sixcarbon atoms, unsubstituted aryloxy groups, halo-substituted aryloxygroups, unsubstituted aralkoxy groups, having halo substituents on thearyl portion thereof, and halogen atoms; Z is selected from the classconsisting of hydrogen and halogen atoms; and wherein at least one ofthe groups represented by R and Z is a group other than hydrogen and B)a compound having the general formula:

I -OH X ll 0 H W wherein X is a non-chromophoric, electron-withdrawingsubstituent and is selected from the class consisting of trifluoroalkylgroups, carbalkoxy groups, the sulfamyl group, N-substituted sulfamylgroups, the carbamyl group, N-substituted carbamyl groups and acylgroups.

8. A light-sensitive diazo composition as claimed in claim 7, whereinthe light-sensitive diazonium compound is 4-morpholino-2.5-diisopropoxybenzenediazonium hexafluorophosphate; thecoupling components are 2,2,4,4'- tetrahydroxy-3,3-dimethyldiphenylsulfide, 2,2,4,4'- tetrahydroxy-5,5'-dichlorodiphenyl sulfide, and2-hydroxy-3- naphthoic acid-(3-acetyl)anilide; and the backgrounddiscoloration inhibitor is l,2,3-triphenylimidazolidine.

9. A light-sensitive diazo composition as claimed in claim 7, whereinthe light-sensitive diazonium compound is 4-morpholino-2,S-diisopropoxybenezenediazonium hexafluorophosphate; thecoupling components are 2,2,4,4'- tetrahydroxy-3,3'-dimethyldiphenylsulfide, 2,2,4,4'- tetrohydroxy-5,5'-dichlorodiphenyl sulfide, and2-hydroxy-3- naphthoic acid-(3-acetyl)anilide; and the backgrounddiscoloration inhibitor is N ,N'-diphenylethylene diamine.

10. A light-sensitive diazo composition as claimed in claim 7, whereinthe light-sensitive diazonium compound is 4-morpholino-2,5-diisopropoxybenzenediazonium hexafluorophosphate; thecoupling compounds are 2,2,4,4'- tetrahydroxy-3,3'-dimethyldiphenylsulfide, 2,2,4,4'- tetrahydroxy-5,5'-dichlorodiphenyl sulfide, and2-hydroxy-3- naphthoic acid-(3'-acetyl)anilide, and the backgrounddiscoloration inhibitor is N ,N-di( p-tolyl)ethylene diamine.

11. A light-sensitive diazo composition as claimed in claim 7, whereinthe light-sensitive diazonium compound is 4-morpholino-2,5-diisopropoxybenzenediazonium hexafluorophosphate; thecoupling components are 2,2,4,4'- tetrahydroxy-3,3-dimethyldiphenylsulfide, 2,2,4,4'- tetrahydroxy-5,5-dichlorodiphenyl sulfide, and2-hydroxy-3- naphthoic acid-(3-acetyl)anilide; and the backgrounddiscoloration inhibitor is N ,N-di( m-tolyl)ethylene diamine.

12. A light-sensitive diazo composition as claimed in claim 7, whereinthe light-sensitive diazonium compound is 4-morpholino-2,S-diisopropoxybenezenediazonium hexafluorophosphate; thecoupling components are 2,2,4,4'- tetrahydroxy-3 ,3 '-dimethyldiphenylsulfide, 2 ,2 ,4 ,4 tetrahydroxy-5,5-dichlorodiphenyl sulfide, and2-hydroxy-3- naphthoic acid-(3'-acetyl)anilide; and the backgrounddiscoloration inhibitor is 1,3-di(p-tolyl )-2-phenylimidazolidine.

13. A light-sensitive diazo composition as claimed in claim 7, whereinthe light-sensitive diazonium compound is4morpholino-2,5-diisopropoxybenzendiazonium hexafluorophosphate; thecoupling components are 2,2',4,4- tetrahydroxy-3 ,3 -dimethyldiphenylsulfide, 2,2 tetrahydroxy-5,5' -dichlorodiphenyl sulfide, and2-hydroxy-3- naphthoic acid-(3'-acetyl)anilide; and the backgrounddiscoloration inhibitor is l,3-di( m-tolyl )-2-phenylimidizolidine.

14. A light-sensitive diazo composition as claimed in claim 7, whereinthe light-sensitive diazonium compound is 4-morpholino-Z,S-diisopropoxybenzenediazonium hexafluorophosphate; thecoupling components are 2,2,4,4'- tetrahydroxy-3 ,3 -dimethyldiphenylsulfide; 2,2 ,4 ,4 tetrahydroxy-5,5-dichlorodiphenyl sulfide,2-hydroxy-3- naphthoic acid (3'-sulfonamide) anilide; and 2-hydroxy 3naphthoic acid (3[N-methyl]sulfonamido)anilide; and the backgrounddiscoloration inhibitor is 1,2,3-triphenylimidazolidine.

15. A lightsensitive diazo composition as claimed in claim 7, whereinthe light-sensitive diazonium compounds is 4-morpholino-2,5-diisopropoxybenzenediazoniurn hexafluorophosphate, thecoupling components are 2,2,4,4'- tetrahydroxy-3,3-dimethyldiphenylsulfide and 2-hydroxy-3- naphthoic acid (3-acetyl)anilide, and thebackground discoloration inhibitor is l,2,3-triphenylimidazolidine.

16. A light-sensitive diazo composition as claimed in claim 7, whereinthe light-sensitive diazonium compound is 4-morpholino-2,5-diisopropoxybenezenediazonium hexafluorophosphate, thecoupling components are 2,2',4,4- tetrahydroxy-3,3'-dimethyl sulfoxideand 2-hydroxy-3- naphthoic acid (3-acetyl)anilide, and the backgrounddiscoloration inhibitor is l,2,3-triphenylimidazolidine.

17. A light-sensitive diazo composition as claimed in claim 7, whereinthe light-sensitive diazonium compound is 4-morpholino-2,5-diisopropoxybenzene diazonium hexafluorophosphate, thecoupling components are 2,2',4,-tetrahydroxy-3,3'-dimethyl-5,5-dichlorodiphenyl sulfide and2-hydroxy-3naphthoic acid (3-acetyl)anilde and background discolorationinhibitor is 1,2,3-triphenylimidazoliclne.

18. A light-sensitive diazo composition as claimed in claim 7, whereinthe light-sensitive diazonium compound is 4-morpholino-2,5-disopropoxybenaenediazonium hexafluorophosphate, thecoupling components are diresorcyl sulfide and 2-hydroxy-3 naphthoicacid (3'-acetyl)anilide, and the background discoloration inhibitor is1,2,3-triphenylimidazolidine.

19. A light-sensitive diazo composition as claimed in claim 7, whereinthe light sensitive diazonium compound is 4morpholineo-2,5-diisopropoxybenzenediazonium hexafluorophosphate, thecoupling components are diresorcyl sulfoxide and 2-hydroxy-3-naphthoicacid (3'-acetyl)anilide, and the background discoloration inhibitor is1,2,3-triphenylimidazolidine.

20. A light-sensitive diazo composition as claimed in claim 7, whereinthe light-sensitive diazonium compound is 4-morpholino-2,S-diisopropoxybenzenediazpmoi, hexafluorophosphate, thecoupling components are diresorcinol and 2-hydroxy-3-naphthoicacid(3'-acetyl) anilide, and the background discoloration inhibitor is1,2,3-triphenylimidazolidine.

21. A light-sensitive diazo composition as claimed in claim 7, whereinthe light-sensitive diazonium compound is 4-morpholineo-2,5dicyclopentyloxybenzene diazonium hexafluorophosphate,the coupling components are 2,2',4,4'-tetrahydroxy-3,3'-dimethyl-5,5'-dichlorodiphenyl sulfide and2-hydroxy-3-naphthoic acid( 3 -acetyl )lide, and the backgrounddiscoloration inhibitor is l,2,3-triphenylimidazolidine.

22. -tetrahydroxylight-sensitive diazo composition as claimed in claim7, wherein the light-sensitive diazonium comthe pound is 4-morpholineo-2,5-di(secondary-butoxy)benzene diazonium hexafluorophosphate, thecoupling components are 2,2,4,4-tetrahydroxy-3,3-diemthyl5,5'-dichlorodiphenyl sulfide and 2-hydroxy-3-naphthoic acid(3-acetyl)anilide, and the background discoloration inhibitor is1,2,3-triphenylimidazolidine.

23. A diaztotype material comprising a support and a diazo layer coatedon said support, said layer comprising the lightsensitive diazocomposition claimed in claim 1.

24. A diazotype material as claimed in claim 23, wherein the support isselected from the class consisting of paper, cloth, transparentizedpaper, a cellulose ether film a cellulose ester film and a polyesterfilm having a subcoat thereon of cellulose acetate butyrate.

25. A diazotype material comprising a cellulose diacetate film as asupport and a diazo layer coated on said support, said layer comprisingthe light-sensitive diazo composition claimed in claim 8.

26. A diazotype material comprising a cellulose diacetate film as asupport and a diazo layer coated on said support, said layer comprisingthe light-sensitive diazo composition claimed in claim 9.

27. A diazotype material comprising a cellulose diacetate film as asupport and a diazo layer coated on said support, said layer comprisingthe light-sensitive diazo composition claimed in claim 10.

28. A diazotype material comprising a cellulose diacetate film as asupport and a diazo layer coated on said support, said layer comprisingthe light-sensitive diazo composition claimed in claim 11.

29. A diazotype material comprising a cellulose diacetate film as asupport and a diazo layer coated on said support, said layer comprisingthe light-sensitive diazo composition claimed in claim 12.

30. A diazotype material comprising a cellulose diacetate film as asupport and diazo layer coated on said support, said layer comprisingthe light-sensitive diazo composition claimed in claim 13.

31. A diazotype material comprising a cellulose diacetate film as asupport and a daizo layer coated on said support, said layer comprisingthe light-sensitive diazo composition claimed in claim 14. I

32. A diazotype material comprising a cellulose diacetate film as asupport and a diazo layer coated on said support, said layer comprisingthe light-sensitive diazo composition claimed in claim 15.

33. A diazotype material comprising a cellulose diacetate film as asupport and a diazo layer coated on said support, said layer comprisingthe light-sensitive diazo composition claimed in claim 16.

34. A diazotype material comprising a cellulose diacetate film as asupport and a diazo layer coated on said support, said layer comprisingthe light-sensitive diazo composition claimed in claim 17.

35. A diazotype material comprising a cellulose diacetate film as asupport and a diazo layer coated on said support, said layer comprisingthe light-sensitive diazo composition claimed in claim 18.

36. A diazotype material comprising a cellulose diacetate film as asupport and a diazo layer coated on said support, said layer comprisingthe light-sensitive diazo composition claimed in claim 19.

37. A diazotype material comprising a cellulose diacetate film as asupport and a diazo layer coated on said support, said layer comprisingthe light-sensitive diazo composition claimed in claim 20.

38. A diazotype material comprising a cellulose diacetate film as asupport and a diazo layer coated on said support, said layer comprisingthe light-sensitive diazo composition claimed in claim 21.

39. A diazotype material comprising a cellulose diacetate film as asupport and a diazo layer coated on said support, said layer comprisingthe light-sensitive diazo composition claimed in claim 21.

zg gy UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,619,191 Dated November 9, 1971 I Robert C. Desjarlais Page 1 of 9 Itis certified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

In the Specification:

Column 1, line 75, "diazotypec" should read diazotype-.

Column 3, line 48, "4-morpholine" should read --4morpholino--.

Column 3, line 49, insert the following: (isopropoxy) benzene-diazoniumchloride-.

Column 4, line 7, "cenzene" should read --benzene--.

Column 4, line 70, after "acid," and before "2 hydroxy" insert 2hydroxy-B naphthoic anilide--.

Column 4, lines 71 and 72, delete "2 hydroxy-3 naphthoic- (4 chloro)anilide,".

Column 5, line 16, "l-(Benzen 4' sulfonic acid)" should read l-(Benzene-4' sulphonic acid) Column 5, line 19, delete"N,Ndiaryl-substituted" and insert therefor --in.

Column 5, line 21, delete "diazotype" and insert therefor -general-.

Cont. J

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Pacgnt n 3,619,191Band November 9, 1971 nventor) Robert C. Desjarlais P 2 f 9 It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Column 5, line 56, delete "onto" and insert therefor --are-.

Column 6, line 44, after "as" and before ",4,4"', insert Column 6, line45, before ",4,4'" (both occurrences) insert -2,2'.

Column 6, line 46, "5,5' should read -5,5'--.

Column 6, line 47, before ",4,4"', insert --2,2'-.

Column 6, line 60, after "of" and before ",4,4" insert Column 7, line 6,after "2,2',4,4'" and before "3,3'-",

insert tetrahydroxy Column 7, line 14, after "24" and before "then",insert -hours.

Column 7, line 19, "22',4,4'-tetrahydroxy" should read-2,2,4,4'-tetrahydroxy--.

Column 7, line 21, after and before "5.15," insert "'Hydrogen-- Cont J3,619 ,191 November 9, 1971 Patent No. Dated Robert C. Desjarlais Page 3of 9 Inventofls) It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

Column 7, line 23, after "2,2',4,4"' and before "5,5',"

insert tetrahydroxy- Column 7, line 44, after "'2,2',4,4"' and before"5,5'",

insert tetrahydroxy- Column 7, line 53, after "2,2',4,4'" and before"3,3'",

insert tetrahydroxy- Column 7, line 70, delete "5.55" and inserttherefor Column 12, line 39, insert -4.23% in the column under "Found";and delete the number or numbers which appear in the column under"Theoretical" and insert therefor --4.l0%-.

Column 12, line 73, "n" should read m-.

Column 12, line 74, "trifluoromethyl) should read (trifluoromethyl)-.

Column 14, line 21, "ro" should read -or--.

Column 14, line 24, after "to" (first occurrence) and before "five",insert ---about-.

'- Cont.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No,3,619,191 Dated November 9, 1971 Inventor) Robert C. Desjarlais P 4 of'9 It is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 16, line 58, "as" should read -was.

Column 16, line 66, insert ll.63-- in the column under "Found"; anddelete the number or numbers which appear in the column under"Theoretical" and insert therefor --ll.66--.

Column 17, line 26, "N,N" should read -N,N'.

Column 17, line 53, "Triphenylimidazolidene" should readTriphenylimidazolidine.

Column 18, line 29, "illustrated" should read --illustrat e.

Column 18, line '39, delete "g." which appears under the column entitled"AMOUNT".

Column 18, line 46, "2Hydroxy" should read --2Hydroxy.

Column 18, line 63, delete the word "imidazolidine".

Column 19, line 1, "5" should read -4-.

Column 19, line 4, "dimethylethylene" should read --diphenylethylene-.

Column 19, line 28, "0.6g." should read -0.6 cc.-.

Column 19, line 32, "(3' [N" should read (3'[N Cont J UNITED STATESPATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 36l9 Dated November1971 Inventor) Robert C. Desjarlais p 5 f 9 It is certified that errorappears in the above-identified patent and that said Letters Patent arehereby corrected as shown below:

Column 19, line 34, "2,2"" should read -2,2' ,4,4'

Column 19, line 36, "hexfluorophosphate" should read-hexafluorophosphate-.

Column 19, line 55, "0.6g." should read -0.3gm..

Column 19, line 58, "0.759" should be relocated so that it appears underthe column entitled "AMOUNT" Column 19, line 70, "2,2',4,4"' should read2,2',4,4'

tetrahydroxy- Column 19, line 71, "2,2',4,4'3,3'-dimethyl5,5'dichlorodiphenyl" should read 2,2',4,4'tetrahydroxy3,3'dimethyl5,5'-' dichlorodiphenyl In the Claims:

Claim 1, lines 3 and 4 (Column 20, lines 19 and 20) [derived from adialkoxy subsitituted p-phenylene diamine] should be deleted.

L Cont. J

Fo-w UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,619,191 Dated November 9, 1971 Inventor) Robert C. Desjarlais Page 6of 9 It is certified that error appears in the above-identified patentand that said Letters Patent are hereby corrected as shown below:

Claim 1, on the line on which the fourth structural formula begins(Column 20, line 54), insert (3)- on the left-hand edge of the column. I

Claim 1, on the line on which the fifth structural formula begins(Column 20, line 59), insert -(4) on the left-hand edge of the column. I2

Claim 1, last line (Column 20, line 68), after "atoms" and before insertthe following: or a group represented by Ar; and R is a methylene groupor an aryl-substituted methylene group; and

D. an acidic stabilizer.

Claim 2, lines 2 to 6 (Column 20, lines 70 to 74) [derived from4-morpholino2,5-diisopropoxyaniline, 4-morpholino2,5

di (tertiary butoxy) aniline; 4-morpholino-2,5di (secondary butoxy)aniline; or 4-morpholino-2,5-dicyclo-pentoxyaniline]" should be deleted.

Claim 3, line 8 (Column 21, line 11), "1,2,3 triphenylimidazolidene"should read -l,2,3-triphenylimidazolidine.

Cont.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No. 3,619Dated November 9, 1971 Inventor) Robert C. Desjarlai's p 7 f 9 It iscertified that error appears in the above-identified patent and thatsaid Letters Patent are hereby corrected as shown below:

Claim 3, line 9 (Column 21, line 12) ylimidazolidene" should readylimidazolidine, and "1,3-di (p-tolyl)" should read l,3-di(p-tolyl)--.

Claim 3, line 10 (Column 21, line 13) "methylimidazolidene" should read--methylimidazolidine, and "1,2,3 triphenyl 4" should read--l,2,3triphenyl4.

Claim 4, line 2 (Column 21, line 17) after "the" and before "compound"insert --coupling components for the diazonium.

Claim 8, line 3 (Column 22, line 37) "2.5" should read Claim 9, line 6(Column 22, line 48), "tetrohydroxy" should read --tetrahydroxy.

Claim 13, line 3 (Column 23, line 4) "4 morpholino" should read-4-morpholino.

Claim 13, line 5 (Column 23, line 6) "2,2"" should read Cont

2. A light-sensitive diazo composition as claimed in claim 1 wherein thelight-sensitive diazonium compound is (derived from4-morpholino-2,5-diisopropoxyaniline, 4-morpholino-2,5-di(tertiarybutoxy) aniline; 4-morpholino-2,5-di(secondary butoxy) aniline; or4-morpholino-2,5-dicyclopentoxyaniline) a4-morpholino-2,5-di(isopropoxy) benzene diazonium salt, a4-morpholino-2,5-di(tertiary butoxy) benzene diazonium salt, a4-morpholino-2,5-di(secondary butoxy) benzene diazonium salt or a4-morpholino-2,5-di(cyclopentoxy) benzene diazonium salt.
 3. Alight-sensitive diazo composition as claimed in claim 2 which comprisesas a background discoloration inhibitor at least one compound selectedfrom the class consisting of N,N''-diphenylethylenediamine,N,N''di(m-tolyl) ethylene diamine, N, N''di(p-tolyl) ethylenediamine,N,N''diphenylpropylenediamine, N, N''diphenyl-2,3-butylenediamine,N,N''-diphenyl-1,2-butylenediamine, N,N''-diphenylstyrenediamine, 1,2,3triphenylimidazolidene, 1,3-di-(m-tolyl)-2-phenylimidazolidene, and1,3-di(p-tolyl)-2-phenylimidazolidene,1,2,3-triphenyl-4-methylimidazolidene,1,2,3triphenyl4,5-dimethylimidazolidine, 1,2,3-triphenyl-4-ethylimidazolidine, and1,2,3,4-tetraphenylimidazolidine.
 4. A light-sensitive diazo compositionas claimed in claim 3, wherein at least one of the compound is acompound having the general formula selected from the class consistingof:
 5. A light-sensitive diazo composition as claimed in claim 4 whereinR4 is methyl.
 6. A light-sensitive diazo composition as claimed in claim3 wherein at least one of the coupling components for the diazoniumcompound is a compound having the general formula:
 7. A Light-sensitivediazo composition as claimed in claim 3 wherein the coupling componentfor the diazonium compound is a mixture of A) a compound having thegeneral formula selected from the class consisting of:
 8. Alight-sensitive diazo composition as claimed in claim 7, wherein thelight-sensitive diazonium compound is4-morpholino-2.5-diisopropoxybenzenediazonium hexafluorophosphate; thecoupling components are 2,2'',4,4''-tetrahydroxy-3,3''-dimethyldiphenylsulfide, 2,2'',4,4''-tetrahydroxy-5,5''-dichlorodiphenyl sulfide, and2-hydroxy-3-naphthoic acid-(3''-acetyl)anilide; and the backgrounddiscoloration inhibitor is 1, 2,3-triphenylimidazolidine.
 9. Alight-sensitive diazo composition as claimed in claim 7, wherein thelight-sensitive diazonium compound is 4-morpholino-2,5-diisopropoxybenezenediazonium hexafluorophosphate; the couplingcomponents are 2,2'',4,4''-tetrahydroxy-3,3''-dimethyldiphenyl sulfide,2,2'',4,4''-tetrohydroxy-5,5''-dichlorodiphenyl sulfide, and2-hydroxy-3-naphthoic acid-(3''-acetyl)anilide; and the backgrounddiscoloration inhibitor is N,N''-diphenylethylene diamine.
 10. Alight-sensitive diazo composition as claimed in claim 7, wherein thelight-sensitive diazonium compound is 4-morpholino-2,5-diisopropoxybenzenediazonium hexafluorophosphate; the couplingcompounds are 2,2'',4,4''-tetrahydroxy-3,3''-dimethyldiphenyl sulfide,2,2'',4,4''-tetrahydroxy-5,5''-dichlorodiphenyl sulfide, and2-hydroxy-3-naphthoic acid-(3''-acetyl)anilide, and the backgrounddiscoloration inhibitor is N,N''-di(p-tolyl)ethylene diamine.
 11. Alight-sensitive diazo composition as claimed in claim 7, wherein thelight-sensitive diazonium compound is 4-morpholino-2,5-diisopropoxybenzenediazonium hexafluorophosphate; the couplingcomponents are 2,2'',4,4''-tetrahydroxy-3,3''-dimethyldiphenyl sulfide,2,2'',4,4''-tetrahydroxy-5,5''-dichlorodiphenyl sulfide, and2-hydroxy-3-naphthoic acid-(3''-acetyl)anilide; and the backgrounddiscoloration inhibitor is N,N''-di(m-tolyl)ethylene diamine.
 12. Alight-sensitive diazo composition as claimed in claim 7, wherein thelight-sensitive diazonium compound is 4-morpholino-2,5-diisopropoxybenezenediazonium hexafluorophosphate; the couplingcomponents are 2,2'',4,4''-tetrahydroxy-3,3''-dimethyldiphenyl sulfide,2,2'',4,4''-tetrahydroxy-5,5''-dichlorodiphenyl sulfide, and2-hydroxy-3-naphthoic acid-(3''-acetyl)anilide; and the backgrounddiscoloration inhibitor is 1,3-di(p-tolyl)-2-phEnylimidazolidine.
 13. Alight-sensitive diazo composition as claimed in claim 7, wherein thelight-sensitive diazonium compound is 4morpholino-2,5-diisopropoxybenzendiazonium hexafluorophosphate; the couplingcomponents are 2,2'',4,4''-tetrahydroxy-3,3''-dimethyldiphenyl sulfide,2,2-tetrahydroxy-5,5'' -dichlorodiphenyl sulfide, and2-hydroxy-3-naphthoic acid-(3''-acetyl)anilide; and the backgrounddiscoloration inhibitor is 1,3-di(m-tolyl)-2-phenylimidizolidine.
 14. Alight-sensitive diazo composition as claimed in claim 7, wherein thelight-sensitive diazonium compound is 4-morpholino-2,5-diisopropoxybenzenediazonium hexafluorophosphate; the couplingcomponents are 2,2'',4,4''-tetrahydroxy-3,3''-dimethyldiphenyl sulfide;2,2'',4,4''-tetrahydroxy-5,5''-dichlorodiphenyl sulfide,2-hydroxy-3-naphthoic acid (3''-sulfonamide) anilide; and 2-hydroxy3-naphthoic acid (3''(N-methyl)sulfonamido)anilide; and the backgrounddiscoloration inhibitor is 1,2,3-triphenylimidazolidine.
 15. Alight-sensitive diazo composition as claimed in claim 7, wherein thelight-sensitive diazonium compounds is4-morpholino-2,5-diisopropoxybenzenediazonium hexafluorophosphate, thecoupling components are 2,2'',4,4''-tetrahydroxy-3,3''-dimethyldiphenylsulfide and 2-hydroxy-3-naphthoic acid (3''-acetyl)anilide, and thebackground discoloration inhibitor is 1, 2,3-triphenylimidazolidine. 16.A light-sensitive diazo composition as claimed in claim 7, wherein thelight-sensitive diazonium compound is 4-morpholino-2,5-diisopropoxybenezenediazonium hexafluorophosphate, the couplingcomponents are 2,2'',4,4''-tetrahydroxy-3,3''-dimethyl sulfoxide and2-hydroxy-3-naphthoic acid (3''-acetyl)anilide, and the backgrounddiscoloration inhibitor is 1,2,3-triphenylimidazolidine.
 17. Alight-sensitive diazo composition as claimed in claim 7, wherein thelight-sensitive diazonium compound is 4-morpholino-2,5-diisopropoxybenzene diazonium hexafluorophosphate, the couplingcomponents are2,2'',4,''-tetrahydroxy-3,3''-dimethyl-5,5''-dichlorodiphenyl sulfideand 2-hydroxy-3naphthoic acid (3''-acetyl)anilde and the backgrounddiscoloration inhibitor is 1,2, 3-triphenylimidazoliclne.
 18. Alight-sensitive diazo composition as claimed in claim 7, wherein thelight-sensitive diazonium compound is 4-morpholino-2,5-disopropoxybenaenediazonium hexafluorophosphate, the couplingcomponents are diresorcyl sulfide and 2-hydroxy-3 naphthoic acid(3''-acetyl)anilide, and the background discoloration inhibitor is1,2,3-triphenylimidazolidine.
 19. A light-sensitive diazo composition asclaimed in claim 7, wherein the light sensitive diazonium compound is4-morpholineo-2,5-diisopropoxybenzenediazonium hexafluorophosphate, thecoupling components are diresorcyl sulfoxide and 2-hydroxy-3-naphthoicacid (3''-acetyl)anilide, and the background discoloration inhibitor is1,2,3-triphenylimidazolidine.
 20. A light-sensitive diazo composition asclaimed in claim 7, wherein the light-sensitive diazonium compound is4-morpholino-2, 5-diisopropoxybenzenediazpmoi, hexafluorophosphate, thecoupling components are diresorcinol and 2-hydroxy-3-naphthoicacid(3''-acetyl) anilide, and the background discoloration inhibitor is1, 2,3-triphenylimidazolidine.
 21. A light-sensitive diazo compositionas claimed in claim 7, wherein the light-sensitive diazonium compound is4-morpholineo-2,5dicyclopentyloxybenzene diazonium hexafluorophosphate,the coupling components are 2,2'',4,4''-tetrahydroxy-3,3''-dimethyl-5,5''-dichlorodiphenyl sulFide and 2-hydroxy-3-naphthoicacid(3''-acetyl)lide, and the background discoloration inhibitor is1,2,3-triphenylimidazolidine.
 22. -tetrahydroxy-light-sensitive diazocomposition as claimed in claim 7, wherein the light-sensitive diazoniumcompound is 4-morpholineo-2,5-di(secondary-butoxy)benzene diazoniumhexafluorophosphate, the coupling components are2,2'',4,4''-tetrahydroxy-3,3''-diemthyl 5,5''-dichlorodiphenyl sulfideand 2-hydroxy-3-naphthoic acid (3''-acetyl)anilide, and the backgrounddiscoloration inhibitor is 1,2,3-triphenylimidazolidine.
 23. Adiaztotype material comprising a support and a diazo layer coated onsaid support, said layer comprising the light-sensitive diazocomposition claimed in claim
 1. 24. A diazotype material as claimed inclaim 23, wherein the support is selected from the class consisting ofpaper, cloth, transparentized paper, a cellulose ether film a celluloseester film and a polyester film having a subcoat thereon of celluloseacetate butyrate.
 25. A diazotype material comprising a cellulosediacetate film as a support and a diazo layer coated on said support,said layer comprising the light-sensitive diazo composition claimed inclaim
 8. 26. A diazotype material comprising a cellulose diacetate filmas a support and a diazo layer coated on said support, said layercomprising the light-sensitive diazo composition claimed in claim
 9. 27.A diazotype material comprising a cellulose diacetate film as a supportand a diazo layer coated on said support, said layer comprising thelight-sensitive diazo composition claimed in claim
 10. 28. A diazotypematerial comprising a cellulose diacetate film as a support and a diazolayer coated on said support, said layer comprising the light-sensitivediazo composition claimed in claim
 11. 29. A diazotype materialcomprising a cellulose diacetate film as a support and a diazo layercoated on said support, said layer comprising the light-sensitive diazocomposition claimed in claim
 12. 30. A diazotype material comprising acellulose diacetate film as a support and diazo layer coated on saidsupport, said layer comprising the light-sensitive diazo compositionclaimed in claim
 13. 31. A diazotype material comprising a cellulosediacetate film as a support and a daizo layer coated on said support,said layer comprising the light-sensitive diazo composition claimed inclaim
 14. 32. A diazotype material comprising a cellulose diacetate filmas a support and a diazo layer coated on said support, said layercomprising the light-sensitive diazo composition claimed in claim 15.33. A diazotype material comprising a cellulose diacetate film as asupport and a diazo layer coated on said support, said layer comprisingthe light-sensitive diazo composition claimed in claim
 16. 34. Adiazotype material comprising a cellulose diacetate film as a supportand a diazo layer coated on said support, said layer comprising thelight-sensitive diazo composition claimed in claim
 17. 35. A diazotypematerial comprising a cellulose diacetate film as a support and a diazolayer coated on said support, said layer comprising the light-sensitivediazo composition claimed in claim
 18. 36. A diazotype materialcomprising a cellulose diacetate film as a support and a diazo layercoated on said support, said layer comprising the light-sensitive diazocomposition claimed in claim
 19. 37. A diazotype material comprising acellulose diacetate film as a support and a diazo layer coated on saidsupport, said layer comprising the light-sensitive diazo compositionclaimed in claim
 20. 38. A diazotype material comprising a cellulosediacetate film as a support and a diazo layer coated on said support,said layer comprising the light-sensitive diazo composition claimed inclaim
 21. 39. A diazotype material comprising a cellulose diacetate filmas a support and a diazo layer coated on said support, said lAyercomprising the light-sensitive diazo composition claimed in claim 21.